Alkyl phenol formaldehyde resin esters



Unite States ate 2,391,021 Patented June 16, 1959 ALKYL PHENOLFORMALDEHY DE RESIN ESTERS David Aelony, Minneapolis, Minn, assignor toGeneral Mills, 1116., a corporation of Delaware No Drawing. ApplicationApril 26, 1954 Serial No. 425,749

8 Claims. (Cl. 260-19) The present invention relates to esters of alkylsubstituted phenol-formaldehyde resins. The present application is acontinuation-in-part of my co-pending applications Serial No. 300,753filed July 24, 1952 and Serial No. 281,038 filed April 7, 1952, bothabandoned, the latter application being a continuation-in-part of myapplication Serial No. 142,709 filed February 6, 1950, now Patent No.2,649,422.

The esters of the present invention are derived from alkyl substitutedphenol formaldehyde resins and higher unsaturated fatty acids such asthose derived from drying oils or semi-drying oils. The esters areliquid drying oils which dry rapidly to yield hard, tough resilientfilms. The films are resistant to hot and cold water and displayphenomental resistance to aqueous alkali.

It is, therefore, an object of the present invention to provide novelunsaturated higher fatty acids esters of alkyl substitutedphenol-formaldehyde resins of a particular type. It is another object ofthe present invention to provide novel esters of the above type whichare capable of drying tohard, tough, resilient film displaying goodresistance to hot and cold water and aqueous alkali.

The resins employed in the present invention are derived fromformaldehyde and an alkyl substituted phenol in which the alkylsubstituent contains from 1-8 carbon atoms. The phenol may contain asingle alkyl substituent as in the case of cresol or may contain aplurality of sub stituents as in the case of xylenol. The phenol shouldhave two reactive positions available such as the two ortho positions oran ortho and the para position. Typical phenols which are suitable forthe present purposes include cresol, xylenol, ethyl phenol, isopropylphenol, tertiary butyl phenol, tertiary amyl phenol, hexyl, heptyl andoctyl phenols. The substituents may be either straight or-branchedchain.

The phenolic resins contain on the average from 4 to about phenolicgroups in the resin molecule and are substantially free from volatilematerials and particularly from residual phenol and lower molecularweight condensation products such as the condensation productscontaining two phenolic nuclei. a

The reaction of the phenol and the formaldehyde may be carried outeither at atmospheric pressure or under superatmospheric pressure. Thetime required for the condensation varies With the temperature and withthe amount and type of catalyst. As will be seen from the examples,resins made by condensation for from /2 to 7 hours at a 160 C. aresuitable for the present invention. Where a strong catalyst such as HClis employed, a suitable degree of condensation may be obtained in ashorter period of time and at a lower temperature.

After the resinification reaction, the resin is subjected to a treatmentto eliminate low molecular weight condensation products and residualphenol. This may be accomplished by subjecting the resin to a strippingprocess which may conveniently be carried out at temperatures of atleast 250' C. at an absolute pressure of mercury usually in therange of1-5 mm. Preferably, however, under these conditions of vacuum thestripping is carried out until the temperature of2703l 0 C. is attained.At the higher temperatures for stripping somewhat higher pressures maybe tolerated.

In place of subjecting the phenolic resin to a stripping process, theresidual phenol and the low molecular weight condensation products maybe caused to combine with the. rest of the polymer by subjecting the.reaction mixture. to. a further heat treatment orbodying .operation attemperatures between 250 and 300 C. In this process the resin undergoesfurther condensation and thezresidual phenol and thelow molecular weightcondensation products substantially completely react with the rest ofthe resin.

The resins thus obtained are hard brittle resins of light color. Theyare. insoluble in fatty oils and fatty acids. The resins most usefulinthe present invention have a viscosity ranging from approximately 5 toapproximately 35 centistokes in a 30% solution by weight in dimethylformamide. A preferred range of viscosities is 8 to 20 centistokes. Thisviscosity is determined as followst A filtered 30% solution by weight ofthe resin in dimethyl formamide is tested in the Ostwald-Fenske S300viscosimeter at 30 C. using 10 cc. of solution. The time thus obtainediscompared. with the time and viscosity of a National Bureau of Standardsstandard sample. oil K-S to determine the viscosity of. the 30% solutionof the resinsin accordance with the formula:

Viscosity in centistokes =a -lfl0 I B where t,,=time of efilux forpolymer solution d,=density Of standard z,=time of efflux of standard=absolute viscosity of standard, in poises The time of efflux variedfrom 21 to 74 seconds. with th viscosimeter employed. it

The resins above described are esterified with unsaturated higher fattyacids containing from 3-22 carbon atoms. These fatty. acids may besingle isolated fatty acids, or mixtures of fatty. acids derived from adrying or semi-drying 0 1,, r any selected fraction of the mixed acidsof a drying oil or semi-drying oil. Typical drying oil and semi-dryingoil acids. include those from soybean oil, linseed oil, tung oil,perilla oil, oiticica oil, sunflower oil, saillower oil, menhaden oil,and the like. The acids employed for esterification. should have aniodine number of at least and preferably at least 110.

The esterification may be carried out by simply heating/the resins withthe fatty acids at temperatures from about ZOO-275 C. Esterificationcatalysts in general may be employed, but it is preferred to employtriphenyl phosphite as the estenffication catalyst. The time re quiredfor esterification varies widely, depending upon the conditions, but ingeneral, from about 2, to about 10 hours is sufficient time to effect adesired degree of esterification. In order to speed up theesterification reaction it is preferred to employ an excessor" fattyacids over the theoretical quantity of fatty acids necessary forcomplete esterification. The excess fatty acids may then be stripped offby vaporization after the esterification is substantially complete. Theemployment of an excess ofifatty acids not only speeds up the reactionbut also prevents undue polymerization of the fatty acids duringesterification by reducing the time period during which the fatty acidsare subjected to the elevated temperature. When less than completeesterification is desired, substantially the theoretical quantity ofacids for the desired degree of esterification may be used; the excesshydroxyl groups speed up the reaction.

The resins of the present invention are esterified from 50-100% by meansof the unsaturated higher fatty acids. The particular range ofesterification employed depends upon the application to which the estersare to be put. For certain metal primers a degree of esterificationwithin the range of 50-70% has been found to be preferred. For otherapplications higher degrees of esterification on up to completeesterification are preferred.

The esters preferably have relatively low acid numbers. Usually an acidnumber as low as 30 is desired and usually an acid number below 20 oreven below .is preferred. This low acid number may be attained indifferent ways, thus where a relatively low degree of esterification isto be obtained, the esterification may be carried out with about 5080%of the quantity of free .fatty acids which would be required forcomplete esterification. Under these circumstances practically all ofthe free fatty acid may react with the resin and produce an ester ofabout 50-80% esterification and at the same time the ester has a verylow acid number. In other instances, especially where the higher degreesof esterification are desired, it is preferred to employ an excess ofthe acid and then after the desired degree of esterification has beenobtained, the excess acid may be removed by stripping. This strippingmay involve subjecting the ester to a vacuum of, for example, about 1-5mm. of mercury absolute pressure at a temperature ranging from 260-275C. This results in the removal of virtually all unesterified fatty acidsand also removes any other volatile material which may be present. It isapparent that this method of stripping may likewise be applied to lowerdegrees of esterified resins if desired.

In addition to the straight vacuum stripping of the resin and resinesters, other ways of removing the volatile materials may be employed.These methods include steam distillation of the volatile material,solvent extraction as for example with methanol, and in general anyknown method of removing low molecular weight volatile material frompolymeric material.

The products of the present invention may be simple fatty acid esters ofthe phenolic resins or may be mixed fatty and rosin acid esters of theresins. It has been discovered that when a mixture of rosin acids. andthe fatty acids is used for esterification the esters obtained aresuperior in drying rates and the films obtained are superior in hardnessand in alkali resistance. Of the total esterified acids from 10-40% maybe rosin acids. The preferred range is from -30% of rosin acids. Anysource of rosin acids may be employed. However, for the sake of economyit is preferred to employ a commercially available product which is therosin acid fraction resulting from the fractional distillation of theacids of tall oil. These rosin acid fractions may contain from 60-80% ofrosin acids with the balance being predominantly higher fatty acids,mostly unsaturated. The rosin acid fraction of tall oil also contains aminor quantity of unsaponifiable materials. The fatty acid content ofthe rosin acid fraction should be taken into account in bringing therosin acid content of the mixed acid into the range referred to above.In calculating the polymerizability index as hereinafter described therosin acids need not be taken into consideration.

The products which are suitable for the present in- Yention are thosewhich have a polymerizability index ranging from 140 to 1000. Thepolymerizability index is an indication of the molecular weight of theresin employed, as well as the degree of polymerizability of the fattyacids employed for esterification. The polymerizability index is definedas the mathematical product of the viscosity in centistokes at 30 C. ofa 30% by weight solution of the resin in dimethyl formamide aspreviously described, and the viscosity in centistokes ob- '4 tained ona bodied sample of the fatty acids to be employed for esterification.

The method of determining the viscosity of the bodied fatty acids is asfollows: 500 grams of the fatty acids to be employed for esterificationare heated to a temperature of 260 C. under nitrogen and are held atthat temperature for 7 hours. The bodied fatty acids are then cooled to40 C. before being contacted with the atmosphere. The viscosity is thendetermined at 40 C. in the Ostwald-Fenske viscosimeter using 10 cc. ofthe acids. The viscosity of these acids is determined In centistokes bycomparison with a standard in the manner previously described. Ingeneral, the viscosities of the bodied acids range from 20 tocentistokes.

When the mathematical product of the resin viscosity and the bodied acidviscosity (the polymerizability index) falls within the range of to1000, the resin esters are found to possess the desirable propertiespreviously described. When this polymerizability index substantiallyexceeds 1000, the resin ester is likely to be a gel or is likely to gelreadily during application or use. Frequently when it is attempted toprepare a prodnot having a polymerizability index in excess of 1000gelation occurs during the esterification reaction. When thepolymerizability index is below 140, the product 1s found to be of toolow molecular weight and is decidedly inferior in properties,particularly in the alkali stability. A preferred range ofpolymerizability indices is from 280 to 600.

In general, the products of the present invention are characterized byexceptional stability toward aqueous alkali. This has been determined byexposing dried films of the resin esters to 5% aqueous sodium hydroxideat room temperature for extended periods of time. In general, theproducts of the present invention are stable to 5% aqueous sodiumhydroxide for at least 4 hours. Some of the products have not failed in5% aqueous sodium hydroxide even after exposure to this solution for 60or more days. The alkali stability is determined by exposing the filmsdeposited on test tubes to the alkali and at intervals removing thecoated test tube from the aqueous alkaline solution and rubbing itbetween the fingers to determine whether or not the film has softenedenough to fail. For purposes of comparison it may be stated that highquality alkyd resins fail in 5% aqueous alkali in as short a time periodas 20 to 30 minutes.

It should be pointed out that in the past, attempts have been made toesterify phenolic resins. Typical examples of these prior attempts areto be found in Cherry Patent 2,091,965 and Sorenson 2,544,365. In theseprior attempts however, no attempt has been made to adequatelycharacterize the resins which are employed, nor has any attempt beenmade to eliminate low molecular weight materials. Moreover, these priorattempts have relied on acetic anhydride to assist in the esterificationwith the unsaturated higher fatty acids. This necessarily resulted insome acetylation of the resin. The introduction of the acetyl groupsinto the resin impairs the water and alkali resistance of the product.In the present invention reliance is not placed on acetic anhydride andaccordingly acetyl groups are not present in the present product.

Example 1 The following materials were charged into an autoclave:

Grams Para-tertiary-butylphenol 1500 Formalin 813 Oxalic acid 10 Theautoclave was closed and the reaction mixture heated to C. for 5 hours.The autoclave was cooled and the resin was removed. It weighed 2284 g.The resin was stripped by subjecting it to Water pump vacuum and heatingit up to 270 C. to yield a resin having a melting point of 205-225 C.(evacuated tube). The viscosity of a 30% solution of this resin indimethyl formamide was 10.82 centistokes.

162 grams of the above resin, 350g. of the C acids of soybean oil (inthebodied form these acids had. a viscosity of 24.65 centistokes), 3 g.of triphenyl phosphite and50 cc. of xylene were refluxed and agitatedunder a Stark and Dean tube. The temperature was maintained at 260 C.for 4 hours at which time the theoretical quantity of water required for100% of esterification had been obtained. The ester was diluted with 100cc. of xylene, mixed with a filter aid, and was then filtered. Thefiltrate was evaporated and stripped up to a temperature of 275 C. at100 A 60% solution by weight in mineral spirits was-prepared, thesolution containing 0.3% Pb and 0.06% Co as. naphthenates. In this andthe following examples the solution was applied to plates and tubes andthe films were allowed to dry. The dried films were tested, the resultsbeing indicated in the table given hereinafter.

Example 2 162 gramsgof the resin of Example 1, 350 g. of linseed oilfatty acids (bodied viscosity 43.29 centistokes), 3 g. of triphenylphosphite, and 50 cc. of xylene were refluxed and agitated under a Starkand Dean tube at 260 C. for 3 hours 40 minutes, at which timeapproximately the theoretical quantity of water required for completeesterification was obtained. The product was diluted with xylene, mixedwith filter aid, and filtered. The filtrate was evaporated: and strippedto a temperature of 275 C. at 5 A 60% solution in mineral spiritscontainingthe driers previously described was prepared.

Example 3 162 grams of the resin of Example 1, 350 g; dehydrated eastoroil fatty acids (bodied viscosity 70.33 centistokes), 3 g. triphenylphosphite, and 50 cc. of xylene were refluxed and agitated under a Starkand Dean tube at 260 C. for 2% hours, at which time 17.7 cc. of atheoretical quantityof 18 cc. of Water required for completeesterification were obtained. The ester was diluted with xylene, mixedwith filter aid, and filtered. The filtrate was evaporated and strippedto 250 C. at p. The 60% solution in mineral spirits was preparedcontaining driers as previously described.

Example 4 The following materials were charged into an autoclave:

The autoclave was closed and was heated to a temperature of 160 C.andmaintained at that temperature for 3 hours. The autoclave was thencooled to 105 C., at which time the autoclave was opened and theresintransferredto a 5-liter flask. The resin was stripped by evacuating theflask to 10 mm. and heating the resin to a temperature of 275 C. Theresin had a melting point of 174-188 C. and had a viscosity in asolution in dimethyl formamide of 9.58 centistokes.

162 grams of the above resin, 280 g. of the soy acids of Example 1, 3 g.triphenyl phosphite, and 50 cc. of xylene were refluxed and agitatedunder a Stark and Dean tube at 260 C. After 6 hours, 17.25 cc. out of atheoretical 18 cc. required for complete esterification were obtained.The product was stripped by heating to 270 C. at p. A 70% solution inmineral spirits was prepared and filtered. Drier in the form of 0.1% Coas naphthenate on the solids basis was then added.

d Example 5 Grams Para-tertiary-butylphenol 15 00 Formalin 813 Oxalicacid 10 The autoclave was closed and was then heated to 160 C. for7hours. The autoclave was cooled and the resin removed. The resin wasstripped to 270 C. at water pump vacuum to yield a resin which melted at205-225 C. ('evacuated tube). The resinhad a viscosity of 10.75centistokes in a 30% solution :by weight in. dimethyl formamide.

162 grams of the above resin, 350 1g. of the dehydrated castor oil fattyacids ofExample 3, 3 g. triphenyl phosphite, and 50 cc. of xylene wererefluxed and agitated under a Stark and Dean tube at 260 C. for 2 /2hours. At that time 17.5 cc. of atheoretical 18' cc. .required forcomplete esterification were obtained. The product was diluted withxylene, mixed with filter aid, and filtered. The filtrate was evaporatedand strippedto 255 C. at 50 A 60% solution of the stripped ester inmineral spirits was prepared containing 0.1% cobalt as the naphthenateon the solid. basis.

Example 6 162 grams of the resin of ExampleS, 350. g. of the linseed oilfatty acids of Example 2, 3 g. triphenyl phosphite, and 50 cc. of xylenewere refluxed and agitated under aStark and. Dean tube at 260 C. for 4hours. At this time the theoretical quantity of water required forcomplete esterification was obtained. The product was diluted with cc.ofxylene, mixed with filter aid, and filtered. The filtrate wasevaporated and stripped to 275 C. at 25m. A 60% solution in mineralspirits was prepared containing 0.3% Pb and 0.06% Co as naphthenates.

Example 7 The following materials were charged into an autoclave:

The autoclave was closed and the reaction mixture heated up to aboutCafor one-half hour. The autoclave was then cooled and opened and theresin removed. It had a heavy taify consistency and was stripped byheating to 270 C. under water pump vacuum to yield 1060 g. of resin. Theresin had a capillary melting point of 133- 139 C., and'a hydroxylnumber of 390. 887 g. of the resin was further stripped by heating to310 C. at 3 mm. The viscosity of a 30% solution in dimethyl formamidewas 5.98 centistokes.

182 grams of the stripped resin (stripped to 310 C.), 350 g. of thesoybean acids of Example 1, 4 g. triphenyl phosphite, and 50 cc. ofxylene were refluxed and agitated under a Stark and Dean tube at 260 C.for 6 hours. 19.6 cc. of a theoretical 20.2 cc. of water required forcomplete esterification was obtained. The product was evaporated andthen stripped to 260 C. at 30;. A 60% solution of the stripped materialwas prepared inmineral spirits and 0.3% Pb and 0.06% Co were added asnaphthenates. The resultant solution was applied to tubes and plateswith the following results: The films dried to no transfer in 3 hours;dried through in 3% hours; hardness in 24 hours, 14; o.k. in 2 hours ofboiling water; failed in 6 hours in 5% NaOH on rubbing; slight blush incold water in 3 days; hardness in 7 days, 18; the blush recovered; acidnumber 5.1; hydroxyl number 26.1.

Example 8 162 grams of the resin of Example 7, 350 g. of the evaporatedand stripped to 260 C. at 50;.

dehydrated castor oil fatty acids of Example 3, 3 g. of triphenylphosphite, and 50 cc. of xylene were refluxed and agitated under a Starkand Dean tube at 260 C. The theoretical quantity of water required forcomplete esterification was obtained in 3 hrs. The product was A 60%solut-ion in mineral spirits containing 0.3% Pb and 0.06% Co asnaphthenates was prepared. The solution was applied to tubes and plateswhich dried to no transfer in 90 minutes and dried through in 2 /2hours; hardness in 24 hours, 24;-acid number 8.4; hydroxyl number 12.3;o.k. in boiling water after 2 hours immersion; failed in NaOH in 2 days;hardness 8 days, 28; o.k. in cold water in 4 days.

Example 9 The following materials were charged into a flask;

Para-tertiary-butylphenol 'g 600 Formalin g 486 Concentratedhydrochloric acid cc 1 Refluxing was carried on for 1 hour. The reactionwas exothermic at 95 C. After one hour the reaction mixture wasevaporated until a temperature of 220 C. was reached. The temperature of220 C. was main tained for another 30 minutes, at which time the residuehad a melting point of 112.5-117.5 C., a hydroxyl number of 430, and amolecular weight of 600.

An additional batch of this resin was prepared in which an additional 1cc. of hydrochloric acid was added after the first one-half hour ofreaction. Otherwise the reaction was carried on the same to yield aresin having a melting point of 101103.5 C., a hydroxyl number of 435.9,and a molecular weight of 5 81. These two batches of resin were thenmixed and were stripped, first under mm. vacuum, then by heating to 310C. at 2.8 mm. The viscosity of a 30% solution in dimethyl formamide was7.17 centistokes.

162 grams of the above stripped mixture of resin, 350 g. of the linseedoil fatty acids of Example 2, 4 g. triphenyl phosphite, and 50 cc. ofxylene were refluxed and agitated under a Stark and Dean tube at 260 C.for 5 hours, at which time the theoretical quantity of water requiredfor complete esterification was recovered. The product was evaporatedand then stripped to 260 C. at 70;/.. A 50% solution of the strippedmaterial in xylene was prepared and cooled. Driers were added as in thepreceding example. The solution was immediately applied to tubes andplates, which dried to no transfer in minutes, and dried through in 1hour. Films were tack free to foil in '6 hours; hardness in 24 hours,20. The films became etched in boiling water in 2 hours, but recovered.The films blushed very slightly in cold waterin 3 days, but recoveredcompletely. They failed after 10 days immersion in 5% sodium hydroxidesolution. Hardness in 7 days, 34.

Example 10 1200 grams of para-tertiary-hutylphenol, 650 g. of formalin,and 11.2 g. of oxalic acid hydrate were introduced into a stainlesssteel autoclave. The temperature was maintained in the approximate rangeof 150-165 C. for 3 hours. The autoclave was cooled and the resinremoved. 1765 grams of the crude resin was stripped to a temperature of270 C. at 9 mm. The residue weighed 1155 g. The viscosity of a 30%solution in dimethyl formamide was 8.83 centistokes.

162 grams of the above resin, 350 g. of mixed soybean oil fatty, acids,4 g. triphenyl phosphite, and 50 cc. of xylene were refluxed andagitated under a Stark and Dean tube. The temperature was maintained at260 C. for 4 hours, after which the theoretical quantity of waterrequired for complete esterification had been recovered. The product wasstripped to a temperature of 260 C. at 40 A 60% solution in mineralspirits was prepared, the solution containing 0.3% Pb and 0.06% Co asnaphthenates. I

Example 11 Example 12 162 grams of the resin of Example 10, 350 g. ofdehydrated castor oil fatty acids, 4 g. triphenyl phosphite, and 50 cc.of xylene were refluxed and agitated under a Stark and Dean tube. Thetemperature was maintained at 260 C. for 3% hours, after which thetheoretical quantity of water had been collected. The product wasstripped to 260 C. at 130,1. A 60% solution in mineral spirits wasprepared containing 0.3% Pb and 0.06% Co as naphthenates.

Example 13 162 grams of the resin of Example 10, 224 g. of soybean oilfatty acids, 4 g. triphenylphosphite, and 50 cc. of xylene were refluxedand agitated under a Stark and Dean tube. The temperature was maintainedat 260 C. for 5 hours, after which the theoretical quantity of waterrequired for complete esterification of the fatty acids was recovered.The quantity of fatty acids employed was sufficient for esterificationof of the hydroxyl groups in the phenolic resin. The product wasstripped to 260 C. at 4511.. A 60% solution in mineral spirits wasprepared containing 0.3% Pb and 0.06% Co as naphthenates.

' Example 14 162 grams of the resin of Example 5, 350 g. of soybeanacids, 5 g. triphenyl phosphite, and 50 cc. of xylene were refluxed andagitated under a Stark and Dean tube. The temperature was maintainedat260 C. for 4 hours, after which the theoretical quantity of waterrequired for complete esterification was recovered. The product wasstripped to 260 C. at 75 A 60% solution of the ester in mineral spiritswas prepared, the solution containing 0.3% Pb and 0.06% Co asnaphthenates.

Example 15 162 grams of the resin of Example 7, which resin had beensubjected to the second stripping step at a temperature of 310 C. and 3mm. of mercury, 375g. of fish oil fatty acids (Neofat 19), 4 g. oftriphenyl phosphite, and 50 cc. of xylene were refluxed and agitatedunder a Stark and Dean tube. The temperature was maintained at 260 C.for 4 hours, after which approximately 99% of the theoretical quantityof water required for complete esterification was recovered. The productwas stripped to 260 at p. The product was made into a 60% solution inmineral spirits containing 0.3% Pb and 0.06% Co as naphthenates.

' Example 16 A para-tertiary-butylphenol formaldehyde resin was preparedin a 50 gallon autoclave using equimolar quantities ofpara-tertiary-butylphenol and formaldehyde and using oxalic acid as acatalyst in the quantity of 1% by weight based on the weight of thepara-tertiary-butylphenol. The reaction was conducted at C. for 5 hours,after which the resin was stripped to 275 C. at 5 mm. The melting pointof the resin was 178-200 I C. The viscosity of a 30% solution indimethyl formamide was 13.40 centistokes., q

12 pounds of the above resin, 25 pounds, 15, oz. of soybean oil fattyacids, 109 g. of triphenyl phosphite, and 4 liters of xylene wereheatedin a kettle to, 260 C. for 6 hours. The kettle was provid ed with a trapfor removal of by-product water. The product had an acid number of 334.Thereafter aportion .otthe ester was stripped by heating t 26.0 C. at 2mm. The acid value of the stripped mterialwasflfl, p l .7

A portion of the unst'r'ippedesterwas' stirred vigorously for minutes atroom temperaturewithan equal .volume" of methanol. Three suchextractions were. made, after which *the'residual ester had anacid'jnumber' of 6.9. A 60% solution in mineral spiritswas prepared, thesolution containing 0.3% .Pb and 0.06% Co as .naphthenates. f

The properties 'of the films prepar'ed in the preceding examples aretabulated in the following table:

ture was refluxed and agitated under a Stark and Dean tube for -6 hoursat 260 C. Thereafter, the reaction mixture was stripped to a temperatureof about 275 C. at an absolute pressure of approximately 200114. toremove unreacted acids. 30 g. of the stripped product were thendissolved in g.'of mineral spirits and 3 cc. of a solution containing 3%lead and 0.6% cobalt as naphthenates were added. The solution wasapplied to tubes and plates, and the films were allowed to dry. The properties of the esters and of the films produced therefrom The followingmaterials \aiere charged into a one-gallonMonel metal autoclave:

1200 Q par aiaa tr lp aol. 715 g. of a 37% aqueous solution offormaldehyde 11.2 g. of oxalic acid dihydrate The quantity. offormaldehydewas a 10% excess over 354.8 and a melting point of;18 8-193'C. The viscosity t.

of a 30% solution indimethyl formamide was 13.62 centistokes. p v WThree samples of the above resin were esterified, the first with soybeanoil fattyacidssolely,"the second with a mixture of by weight soybean oilfatty acidsfand 30% "by weight of a rosin acid fraction of tall oil con-Exam u No 1 2; l 3 4 i s 6 7 s M.P. of Resin, 0 205225 174-188--..205-225.--- 205-225.... 133.139. Vise. of Resin 10 82 10.82 9 40.75....10.75 5.98. Acids... Castor. Gaston..- Linseed... Castor. Vise. ofBodied Acids 26 45....-- 70.33 70.33 4329.-.-.. 70.33. PolymerizabilityIndex. 4634...--- 761.0 756.0 4654-..-.- 420.6. Hours of esterification2.25 2.50 4 6 3. Acid 1%.... 9.0. 5.7 5.1. 8.4. OH 7%.. 27.0 51.1 26.112.3. Tack free to foil, hrs. 4 5% 24. 24. Hardness in24 hrs "16 14 1816 14 24. Hardness in 7 days 1706days, 18 1a 1 16 18 18 8 (5337s, Failedin 5% NaOH 72 hrs... 50 days..- 18 days. 24 hrs..- 63 days.. 10 days..-6 hrs 2 days. Boiling H20, 2hr. immersion. 0K K OK OK. 0K 0K OK OK. 001dH O,3day immersion" 0K OK Blushed 0K 0K Blush 0K4 4'days, 3 days days.recovered.

Example N 0 9 10 11 12 13 14 15 16 M. P. of Resin, 9 G 158-165;--.-160.--- 155-160-.-. 155-160---- 205425-..- 133-139-- 178-200 Vise. ofResin 7.17""-.. 8. 8. 8.83 .75 98- 13.40. Acids"; Linseed Linseed--.Gaston... Vise ofBodied Aci 43. 43. 9 r 45 Polymerizability Inde3104.-..-- 382.3 Hours of esterification 5 l 4 r as Acids 7.4-. 4.9 OH42.2 0 Tack .free .to foil, hrs a 5 Hardness in 24 hrs 2o 22 Hardness in7 days. 84 '%2 Failed in 5% N aOH 10 days... 24 hrs--- Boiling H O, 2hr.immersiom- Blushed OK.

7 2 hrs., 2-hrs., 2 hrs, recovered. recovered. recovered. a Cold H 0, 3dayimtuersion--- Blushed OK 0K Blushed OK 5 Blushed OK.

3 days, 3 days, days 3 days,

recovered. recovered. recovered.

Example 17 are indicated in the table appearing at the end of theseexamples.

Example 18 Example 19 A crude resin was prepared as described in thepreceding example, except that 20% excess formaldehyde was employed. Thecrude resin Was stripped to 280 C. at 75011.. The product had a hydroxylnumber @323 and a melting point of 193-6 C. The viscosity of a 11 30%solution in dimethyl formamide was 20.63 centistokes.

Three esters were prepared from this resin using the acids and theprocedure described in Example 17. The properties of the products areindicated in the table.

Example 20 A crude resin was prepared as described in the precedingexample except that a 25% excess of formaldehyde was employed. The cruderesin was stripped at 270 C. at 300,11. The product had a hydroxylnumber of 295 and a melting point of 1928 C. The viscosity of a 30%solution in dimethyl formamide was 27.89 centistokes.

- 12 Example .22

acids and a para-tertiary butyl phenolformaldehyde resin. The resin hada viscosity in a 30% solution in dimethyl formamide of 7.32 centistokes.The dehydrated castor oil fatty acids when bodied had a viscosity of70.33 centistokes. 162 g. of the resin, 62 g. of waterwhite gum rosin,294 g. of dehydrated castor oil fatty acids, 4 g. of triphenyl phosphiteand 50 cc. of xylene were refluxed and agitated under a Stark and Deantube for 4 hours at 260 C. The product was stripped to 265 C. at 50 A30% solution was prepared as described in Example 17. The properties areindicated in Three esters were prepared from this resin using the thefollowing table.

Rosin Swerd Rocker Soybean Acids, Acid Acid Hydroxyl Tack Hardness 5%Percent Fraction, N o. N 0. free to NaOH Percent 1011, hrs.

1 day 7 days 100 0 4.2 7.38 18 3 days. 70 6. 2 11. 6 4% 24 36 5 days. 5050 7.0 8. 6 4% 38 42 7 days. Ex. 18: i

100 0 5. 9 18. 3 4% '18 22 3 days. 70 30 8. 7 9.0 4% 28 36 11 days.

.............. 50 10. 4 24. 5 4% 28 38 9 days.

0 9. 2 10. 6 4% 18 20 24 hrs. 30 10.1 18. 6 3% 30 36 24 hrs. 60 12. 013. 4 3% 38 48 ddays.

0v 17.1 14.7 V 6V 12 1s 30 4 22 36 19 days. 50 15. 0 3. 4 40 46 18 days30 18. 0 32. 4 5% 18 28 7 days.

Dehydrated Castor Acids Ex. 22: a

80 20 8.9 21.8 5% 18 24 15 days.

acids and the procedure described in Example 17. The properties of theproducts are indicated in the table.

Example 21 An ester was made from a paraie rtiary-butylphenolformaldehyde and a mixture of soybean oil fatty acids,

and rosin. The resin had a viscosity in a 30% dimethyl fluxed andagitated under a Stark and Dean tube for 6" hours at 260 C. At thistime, approximately 90% of the theoretical quantity of water requiredfor complete A series of additional examples was prepared as previouslydescribed. These products were prepared from the indicated phenol withformaldehyde, the character of the resin and of the esterifying acidbeing shown in the usually below 10. The results shown in the tableindicate that with a variety of resins and a variety of esterifyingacids it is possible to obtain compoundsrelated to those shown intheprevious tables possessing comparable properties. It will be apparentthat numerous other variations may be made within'the' scope of theesterification was obtained. The product was then present disclosure toobtain similar products.

- i Hardness Sample Type Resin Resin Esterlfying Acid Poly. Drying 57NaOH hrs.)

. Vise. Index Time (Min.) 1 I o 3 days 7 days p-t-amyl phenol 19.5 Soy50% 515.8 Tack Free 24 37 OK 336.

Y glgginutes) 2.- (in 5. 5 Dehydrated Cas- 386. s 20 Si. Yellow 168.

23% Rosin S1. haze 336. a p-isopropyl phenol 14.9 Soy 56% 394.1 28 0K336. 4 o-isopropyl phenol... 11. 25 Linseed 487. 0 Brown and hazyo-cresol 27. 5 Soy 100% 627.4 18 2o Li e, hazy brown 6 octyl phenol 10.5 Linseed 100%- 454. 5 15 14 S1. hazy 336. 7. p-t-amyl phenol 11. 9 do515. 2 14 18 sag and yellow 8..."--- Mixed xylenols and creso1s 23.4 Soy100% 618.9 20 20 Brown 24. I V

I hereby claim as my invention: .1. An ester 'of apara-tertiary-butylphenolformaldehyde resin, the resin having beenprepared from said phenol and formaldehyde as the sole reactants, in thepresence of an acid catalyst, said resin being substantially free frommonomeric phenol and lower molecular weight condensation productscontaining two phenolic nuclei, said resin having at least 50% of itshydroxyl groups esterified with acids selected from the group consistingof (1) unsaturated higher fatty acids containg from 8 to 22 carbon atomsand (2) mixtures of said unsaturated higher fatty acids with from 10-40%of rosin acids based on the total weight of the mixture, said esterbeing characterized by a polymerizability index of 140-1000, saidpolymerizability index being the mathematical product of (a) theviscosity in centistokes at 30 C. of a 30% solution by weight of theresin in dimethyl formamide and (b) the viscosity in centistokesobtained on a bodied sample of the unsaturated fatty acids, said esterhaving an acid number below 20.

2. Product according to claim 1 in which the resin employed foresterification is substantially free from material vaporizable at 250 C.at 5 mm. of mercury absolute pressure.

3. Product according to claim 1 in which the resin employed foresterification is substantially free from material vaporizable at 310 C.at 5 mm. of mercury absolute pressure.

4. Product according to claim 1 in which the polymerizability index isbetween 280 and 600.

5. Product according to claim 1 in which the ester is substantially freefrom materials vaporizable at 260 C. at 5 mm. of mercury absolutepressure.

6. Product according to claim 1 in which the hydroxyl groups of theresin are substantially completely esterified with the mixed rosin andunsaturated higher fatty acids.

7. Product according to claim 1 in which the resin has a viscositywithin the range of 5 to centistokes and in which the unsaturated higherfatty acid has a bodied viscosity within the range of 20 to 100centistokes.

8. Product according to claim 1 in which the resin has at least of itshydroxyl groups estcrified With a mixture of rosin acid and unsaturatedhigher fatty acids.

References Cited in the file of this patent UNITED STATES PATENTS2,091,965 Cherry Sept. 7, 1937 2,124,285 Bucherer July 19, 19382,622,071 Harrison Dec. 16, 1952 2,638,458 Wheeler May 12, 19532,649,422 Aelony Aug. 18, 1953 2,676,158 Renfrew Apr. 20, 1954 2,730,511Floyd Jan. 10, 1956

1. AN ESTER OF A PARA-TERTIARY-BUTYLPHENOL FORMALDEHYDE RESIN, THE RESINHAVING BEEN PREPARED FROM SAID PHENOL AND FORMALDEHYDE AS THE SOLEREACTANTS, IN THE PRESENCE OF AN ACID CATALYST, SAID RESIN BEINGSUBSTANTIALLY FREE FROM MONOMERIC PHENOL AND LOWER MOLECULAR WEIGHTCONDENSATION PRODUCTS CONTAINING TWO PHENOLIC NUCLEI, SAID RESIN HAVINGAT LEAST 50% OF ITS HYDROXYL GROUPS ESTERIFIED WITH ACIDS SELECTED FROMTHE GROUP CONSISTING OF (1) UNSATURATED HIGHER FATTY ACIDS CONTAINS FROM8 TO 22 CARBON ATOMS AND (2) MIXTURES OF SAID UNSATURATED HIGHER FATTYACIDS WITH FROM 10-40% OF ROSIN ACIDS BASED ON THE TOTAL WEIGHT OF THEMIXTURE, SAID ESTER BEING CHARACTERIZED BY A POLYMERIZABILITY INDEX OF140-1000, SAID POLYMERIZABILITY INDEX BEING THE MATHEMATICAL PRODUCT OF(A) THE VISCOSITY IN CENTISTOKES AT 30*C. OF A 30% SOLUTION BY WEIGHT OFTHE RESIN IN DIMETHYL FORMAMIDE AND (B) THE VISCOSITY IN CENTISTOKESOBTAINED ON A BODIED SAMPLE OF THE UNSATURATED FATTY ACIDS, SAID ESTERHAVING AN ACID NUMBER BELOW 20.